CN117599240A - Preparation method of procyanidine sugar-loaded stimulated hydrogel - Google Patents
Preparation method of procyanidine sugar-loaded stimulated hydrogel Download PDFInfo
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- 239000000017 hydrogel Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims abstract description 38
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 28
- 239000008103 glucose Substances 0.000 claims abstract description 28
- CWEZAWNPTYBADX-UHFFFAOYSA-N Procyanidin Natural products OC1C(OC2C(O)C(Oc3c2c(O)cc(O)c3C4C(O)C(Oc5cc(O)cc(O)c45)c6ccc(O)c(O)c6)c7ccc(O)c(O)c7)c8c(O)cc(O)cc8OC1c9ccc(O)c(O)c9 CWEZAWNPTYBADX-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229920002414 procyanidin Polymers 0.000 claims abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000001301 oxygen Substances 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 143
- 230000003078 antioxidant effect Effects 0.000 claims description 22
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 19
- 239000003963 antioxidant agent Substances 0.000 claims description 19
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 19
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 claims description 18
- XFZJEEAOWLFHDH-UHFFFAOYSA-N (2R,2'R,3R,3'R,4R)-3,3',4',5,7-Pentahydroxyflavan(48)-3,3',4',5,7-pentahydroxyflavan Natural products C=12OC(C=3C=C(O)C(O)=CC=3)C(O)CC2=C(O)C=C(O)C=1C(C1=C(O)C=C(O)C=C1O1)C(O)C1C1=CC=C(O)C(O)=C1 XFZJEEAOWLFHDH-UHFFFAOYSA-N 0.000 claims description 16
- MOJZMWJRUKIQGL-FWCKPOPSSA-N Procyanidin C2 Natural products O[C@@H]1[C@@H](c2cc(O)c(O)cc2)Oc2c([C@H]3[C@H](O)[C@@H](c4cc(O)c(O)cc4)Oc4c3c(O)cc(O)c4)c(O)cc(O)c2[C@@H]1c1c(O)cc(O)c2c1O[C@@H]([C@H](O)C2)c1cc(O)c(O)cc1 MOJZMWJRUKIQGL-FWCKPOPSSA-N 0.000 claims description 16
- HGVVOUNEGQIPMS-UHFFFAOYSA-N procyanidin Chemical compound O1C2=CC(O)=CC(O)=C2C(O)C(O)C1(C=1C=C(O)C(O)=CC=1)OC1CC2=C(O)C=C(O)C=C2OC1C1=CC=C(O)C(O)=C1 HGVVOUNEGQIPMS-UHFFFAOYSA-N 0.000 claims description 16
- ULVXDHIJOKEBMW-UHFFFAOYSA-N [3-(prop-2-enoylamino)phenyl]boronic acid Chemical compound OB(O)C1=CC=CC(NC(=O)C=C)=C1 ULVXDHIJOKEBMW-UHFFFAOYSA-N 0.000 claims description 14
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 13
- 230000004044 response Effects 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 6
- 238000011065 in-situ storage Methods 0.000 claims 2
- 238000006116 polymerization reaction Methods 0.000 claims 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 239000012467 final product Substances 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 claims 1
- -1 phenylboronic acid compound Chemical class 0.000 claims 1
- 230000008961 swelling Effects 0.000 claims 1
- 206010052428 Wound Diseases 0.000 abstract description 21
- 208000027418 Wounds and injury Diseases 0.000 abstract description 21
- 206010012601 diabetes mellitus Diseases 0.000 abstract description 15
- 230000001684 chronic effect Effects 0.000 abstract description 7
- 230000033228 biological regulation Effects 0.000 abstract description 2
- 230000035876 healing Effects 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract 1
- 230000004936 stimulating effect Effects 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 40
- 239000008367 deionised water Substances 0.000 description 32
- 229910021641 deionized water Inorganic materials 0.000 description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 239000000843 powder Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000010453 quartz Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 239000003642 reactive oxygen metabolite Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 4
- 108010062580 Concanavalin A Proteins 0.000 description 3
- 108010015776 Glucose oxidase Proteins 0.000 description 3
- 239000004366 Glucose oxidase Substances 0.000 description 3
- 230000003064 anti-oxidating effect Effects 0.000 description 3
- 229940116332 glucose oxidase Drugs 0.000 description 3
- 235000019420 glucose oxidase Nutrition 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000029663 wound healing Effects 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000002757 inflammatory effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 150000000180 1,2-diols Chemical class 0.000 description 1
- QGMGHALXLXKCBD-UHFFFAOYSA-N 4-amino-n-(2-aminophenyl)benzamide Chemical compound C1=CC(N)=CC=C1C(=O)NC1=CC=CC=C1N QGMGHALXLXKCBD-UHFFFAOYSA-N 0.000 description 1
- 208000002249 Diabetes Complications Diseases 0.000 description 1
- 208000025865 Ulcer Diseases 0.000 description 1
- 206010048038 Wound infection Diseases 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 230000017531 blood circulation Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 208000016097 disease of metabolism Diseases 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000081 effect on glucose Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 230000005182 global health Effects 0.000 description 1
- 230000003394 haemopoietic effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003345 hyperglycaemic effect Effects 0.000 description 1
- 201000001421 hyperglycemia Diseases 0.000 description 1
- 230000008105 immune reaction Effects 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000003834 intracellular effect Effects 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 208000030159 metabolic disease Diseases 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000002018 overexpression Effects 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 231100000397 ulcer Toxicity 0.000 description 1
- 230000003827 upregulation Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
- A61L26/0009—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form containing macromolecular materials
- A61L26/0014—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form containing macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
- A61L26/0061—Use of materials characterised by their function or physical properties
- A61L26/0066—Medicaments; Biocides
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
- A61L26/0061—Use of materials characterised by their function or physical properties
- A61L26/008—Hydrogels or hydrocolloids
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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Abstract
The invention discloses a preparation method of a procyanidine-loaded sugar-stimulated hydrogel, which integrates procyanidins into a phenylboronic acid-based hydrogel system with sugar-sensitive groups, so that the hydrogel disclosed by the invention has the capabilities of stimulating and removing active oxygen by glucose and accelerating the healing of chronic wounds of diabetes, solves the unintelligitization of the procyanidine oxidation resistance, and realizes the dynamic regulation of the release of procyanidins according to the glucose content in the microenvironment of the diabetes wounds. When the sugar-stimulated hydrogel disclosed by the invention is applied to the wound of a diabetic patient, procyanidine can be released along with the concentration of glucose in the surrounding environment, so that the sugar-stimulated hydrogel can be used for promoting the repair of the wound of the diabetes patient and has a wide application prospect in the treatment of the wound of the diabetes patient.
Description
Technical Field
The invention relates to the technical field of biomedical high molecular materials, in particular to a preparation method of procyanidine sugar-loaded stimulated hydrogel.
Background
Diabetes is a common metabolic disease caused by hyperglycemia in the body, often with many complications. Diabetic wound ulcers are one of the complications of diabetes mellitus, a common and severe chronic wound. Currently, there are about 4.63 hundred million diabetics worldwide, most of which suffer from chronic diabetic wounds, leading to global health problems. Diabetic wounds over-express Reactive Oxygen Species (ROS) in a sustained hyperglycemic microenvironment resulting in upregulation of inflammatory factors and impairment of hematopoietic function, disruption of intracellular balance and entrapment of the wound in an extended inflammatory phase. It is necessary to address the delayed closure of diabetic chronic wounds caused by excessive ROS.
The hydrogel is a polymer network system with a three-dimensional reticular cross-linked structure, and the cross-linked network structure can prevent permeation, so that the hydrogel can be used for loading and releasing medicines, and in addition, the hydrogel is extremely hydrophilic, has good biocompatibility, can provide a moist environment for wounds, accelerates wound healing and reduces pain, so that the hydrogel has been widely applied to wound dressings.
The existing glucose sensitive hydrogel mostly adopts Glucose Oxidase (GOD) and concanavalin A (ConA) as recognition elements, but GOD and ConA can cause immune reaction in vivo, and phenylboronic acid group (PBA) receptor recognition elements can overcome the defects, and PBA and derivatives thereof can be reversibly combined with saccharides with ortho cis-diol structures to form PBA salts, so that the recognition effect on glucose is exerted.
Hydrogel dressings with antioxidant activity have been developed as a very promising rational strategy for the treatment of diabetic chronic wounds, but they do not achieve a dynamic regulation of antioxidant activity according to glucose content in the diabetic wound microenvironment, resulting in that the normal physiological functions of ROS (e.g. prevention of wound infection) are affected to some extent, and thus they are non-intelligent antioxidant hydrogels. Achieving intelligent glucose response antioxidant effects to eliminate ROS over-expression in diabetic wounds remains a formidable challenge.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides an intelligent phenylboronic acid-based glucose response antioxidant hydrogel dressing which can release antioxidant substances according to the concentration of glucose in the surrounding environment of a diabetic chronic wound in real time so as to reduce the content of ROS and accelerate wound healing. The technical scheme adopted by the invention is as follows: a hydrogel dressing capable of recognizing glucose is prepared by using phenylboronic acid, and an antioxidant OPC is added to the hydrogel dressing to play an antioxidant role. When glucose concentration around chronic wounds of diabetes rises, boric acid ester bonds formed by phenylboronic acid and OPC are more sensitive to recognition of glucose and break, so that the phenylboronic acid and OPC are selectively combined with 1, 2-diol in the glucose to form new boric acid ester bonds, and during the process, the OPC is released to reduce excessive secreted ROS around the wounds, so that the healing of the wounds is accelerated.
A preparation method of a procyanidin sugar-loaded stimulated hydrogel comprises the following steps:
step (1): preparing 1MNaOH solution, weighing 0.4g NaOH and dissolving in 10ml deionized water to prepare the aqueous solution;
step (2): preparing a photoinitiator Irgacure 2959, weighing 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone in a dark place, and dissolving in a beaker with 10ml of deionized water;
step (3): pouring 1g of acrylamide into a beaker, weighing 9ml of deionized water into the beaker, placing the beaker on a magnetic stirrer, stirring the beaker to be uniform at 400r/min, and marking the beaker as a solution A;
step (4): weighing a certain amount of 3-acrylamidophenylboronic acid, dissolving the 3-acrylamidophenylboronic acid in 1ml of methanol solution, and pouring the solution into the solution A after the solution is completely dissolved so as to fully mix the solution A;
step (5): taking another 50ml beaker, weighing 1g of polyvinyl alcohol solid, adding 10ml of deionized water, then placing the beaker in a constant-temperature water bath kettle, heating and stirring at 90 ℃ for at least 2 hours, taking out and cooling to room temperature until the solid is completely dissolved and no bubbles exist, and recording the solution at the moment as solution B;
step (6): after the solution in the step (4) is uniformly mixed, the PH is adjusted by the NaOH solution prepared in the step (1), and when the PH meter is measured to be 8.5-10, the dropwise adding of the NaOH solution is stopped;
step (7): after the step (6) is finished, mixing the mixture with the solution B for a period of time, and directly adding procyanidine powder with proper mass for stirring;
and (8) dropwise adding the Irgacure 2959 solution prepared in the step (2) under the dark condition, pouring the solution into two quartz plate molds clamped with a silica gel pad with the thickness of 2cm after all substances in the beaker are dissolved in the solution, and irradiating for more than 5 minutes in an ultraviolet curing box to obtain the gel.
The photoinitiator concentration configured in the step (2) is 1-2 multiplied by 10 -3 g/ml；
The procyanidine content in the step (7) is variable, and the procyanidine can be added at will according to the invention, wherein the conventional dosage in the invention is 0.01g, 0.03g and 0.05g;
in the step (8), the ultraviolet irradiation time is 5min, and the shortest irradiation time is 5min.
The invention has the following benefits compared with the prior art
1. Compared with the prior art, the prepared phenylboronic acid-based glucose response antioxidant intelligent hydrogel dressing has certain self-healing capacity and plasticity, can be better attached to the wound surface, and prevents invasion of other germs.
2. The phenylboronic acid disclosed by the invention not only serves as a functional substance, but also serves as a cross-linking agent, so that other cross-linking components are not required to be added in the preparation process of the phenylboronic acid-based glucose response antioxidant intelligent hydrogel dressing.
3. The antioxidant used in the invention is procyanidine, is a natural polyphenol macromolecular substance, is nontoxic and harmless, has stronger antioxidant free radical removal capability, can resist aging and promote blood circulation, and can lead the wound healing speed to be higher.
4. The glucose response anti-oxidation intelligent hydrogel dressing based on phenylboronic acid prepared by the invention not only performs the functions of identifying glucose and resisting oxidation independently, but also combines the two functions to prepare the anti-oxidation intelligent hydrogel dressing capable of responding to glucose, and the release rate of the anti-oxidation substance is obviously improved when the concentration of glucose is increased.
Detailed Description
The invention is described in further detail below by way of examples. The present embodiment is implemented on the premise of the present technology, and a detailed embodiment and a specific operation procedure are now given to illustrate the inventive aspects of the present invention, but the scope of protection of the present invention is not limited to the following embodiments.
Example 1
A method for preparing a procyanidin sugar-loaded stimulated hydrogel, which specifically comprises the following steps:
step (1) dissolving 0.4g of sodium hydroxide in 10ml of deionized water to prepare sodium hydroxide solution, and storing for later use;
under the light-shielding condition, 0.001g of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone is dissolved in 10ml of deionized water to prepare a photoinitiator Irgacure 2959 solution, and the solution is stored for standby;
step (3) 1g of acrylamide is dissolved in 10ml of deionized water;
step (4) 0.02g of 3-acrylamidophenylboronic acid is dissolved in 1ml of methanol solution;
step (5) mixing the solutions in step (3) and step (4);
step (6) adding 0.01g of procyanidin powder into the solution prepared in the step (5);
step (7) adjusting the PH of the solution in step (6) to 8.5 by using the solution prepared in step (1);
step (8), dropwise adding the solution obtained in step (2) into the solution obtained in step (7) under the light-shielding condition;
step (9), 1g of polyvinyl alcohol is dissolved in 10ml of deionized water, and the solution is placed in a constant-temperature water bath kettle, heated and stirred at 90 ℃ for at least 2 hours, and after being stirred uniformly, the solution is taken out and cooled to room temperature to obtain a polyvinyl alcohol solution;
step (10) under the light-shielding condition, the solution in the step (8) and the solution in the step (9) are mixed with each other;
and (11) after the solution in the step (10) is uniformly mixed, pouring the solution into a specific quartz plate mold with the thickness of 100mm multiplied by 2mm, and placing the mold in an ultraviolet curing box for irradiation for 5min to obtain the phenylboronic acid-based glucose response antioxidant intelligent hydrogel dressing.
Example 2
A method for preparing a procyanidin sugar-loaded stimulated hydrogel, which specifically comprises the following steps:
step (1) dissolving 0.4g of sodium hydroxide in 10ml of deionized water to prepare sodium hydroxide solution, and storing for later use;
under the light-shielding condition, 0.001g of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone is dissolved in 10ml of deionized water to prepare a photoinitiator Irgacure 2959 solution, and the solution is stored for standby;
step (3) 1g of acrylamide is dissolved in 10ml of deionized water;
step (4) 0.03g of 3-acrylamidophenylboronic acid is dissolved in 1ml of methanol solution;
step (5) mixing the solutions in step (3) and step (4);
step (6) adding 0.01g of procyanidin powder into the solution prepared in the step (5);
step (7) adjusting the PH of the solution in step (6) to 8.5 by using the solution prepared in step (1);
step (8), dropwise adding the solution obtained in step (2) into the solution obtained in step (7) under the light-shielding condition;
step (9), 1g of polyvinyl alcohol is dissolved in 10ml of deionized water, and the solution is placed in a constant-temperature water bath kettle, heated and stirred at 90 ℃ for at least 2 hours, and after being stirred uniformly, the solution is taken out and cooled to room temperature to obtain a polyvinyl alcohol solution;
step (10) under the light-shielding condition, the solution in the step (8) and the solution in the step (9) are mixed with each other;
and (11) after the solution in the step (10) is uniformly mixed, pouring the solution into a specific quartz plate mold with the thickness of 100mm multiplied by 2mm, and placing the mold in an ultraviolet curing box for irradiation for 5min to obtain the phenylboronic acid-based glucose response antioxidant intelligent hydrogel dressing.
Example 3
A method for preparing a procyanidin sugar-loaded stimulated hydrogel, which specifically comprises the following steps:
step (1) dissolving 0.4g of sodium hydroxide in 10ml of deionized water to prepare sodium hydroxide solution, and storing for later use;
under the light-shielding condition, 0.002g of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone is dissolved in 10ml of deionized water to prepare a photoinitiator Irgacure 2959 solution, and the solution is stored for standby;
step (3) 1g of acrylamide is dissolved in 10ml of deionized water;
step (4) 0.04g of 3-acrylamidophenylboronic acid is dissolved in 1ml of methanol solution;
step (5) mixing the solutions in step (3) and step (4);
step (6) adding 0.01g of procyanidin powder into the solution prepared in the step (5);
step (7) adjusting the PH of the solution in step (6) to 8.5 by using the solution prepared in step (1);
step (8), dropwise adding the solution obtained in step (2) into the solution obtained in step (7) under the light-shielding condition;
step (9), 1g of polyvinyl alcohol is dissolved in 10ml of deionized water, and the solution is placed in a constant-temperature water bath kettle, heated and stirred at 90 ℃ for at least 2 hours, and after being stirred uniformly, the solution is taken out and cooled to room temperature to obtain a polyvinyl alcohol solution;
step (10) under the light-shielding condition, the solution in the step (8) and the solution in the step (9) are mixed with each other;
and (11) after the solution in the step (10) is uniformly mixed, pouring the solution into a specific quartz plate mold with the thickness of 100mm multiplied by 2mm, and placing the mold in an ultraviolet curing box for irradiation for 5min to obtain the phenylboronic acid-based glucose response antioxidant intelligent hydrogel dressing.
Example 4
A method for preparing a procyanidin sugar-loaded stimulated hydrogel, which specifically comprises the following steps:
step (1) dissolving 0.4g of sodium hydroxide in 10ml of deionized water to prepare sodium hydroxide solution, and storing for later use;
under the light-shielding condition, 0.001g of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone is dissolved in 10ml of deionized water to prepare a photoinitiator Irgacure 2959 solution, and the solution is stored for standby;
step (3) 1g of acrylamide is dissolved in 10ml of deionized water;
step (4) 0.04g of 3-acrylamidophenylboronic acid is dissolved in 1ml of methanol solution;
step (5) mixing the solutions in step (3) and step (4);
step (6) adding 0.03g of procyanidin powder into the solution prepared in the step (5);
step (7) adjusting the PH of the solution in step (6) to 8.5 by using the solution prepared in step (1);
step (8), dropwise adding the solution obtained in step (2) into the solution obtained in step (7) under the light-shielding condition;
step (9), 1g of polyvinyl alcohol is dissolved in 10ml of deionized water, and the solution is placed in a constant-temperature water bath kettle, heated and stirred at 90 ℃ for at least 2 hours, and after being stirred uniformly, the solution is taken out and cooled to room temperature to obtain a polyvinyl alcohol solution;
step (10) under the light-shielding condition, the solution in the step (8) and the solution in the step (9) are mixed with each other;
and (11) after the solution in the step (10) is uniformly mixed, pouring the solution into a specific quartz plate mold with the thickness of 100mm multiplied by 2mm, and placing the mold in an ultraviolet curing box for irradiation for 8min to obtain the phenylboronic acid-based glucose response antioxidant intelligent hydrogel dressing.
Example 5
A method for preparing a procyanidin sugar-loaded stimulated hydrogel, which specifically comprises the following steps:
step (1) dissolving 0.4g of sodium hydroxide in 10ml of deionized water to prepare sodium hydroxide solution, and storing for later use;
under the light-shielding condition, 0.001g of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone is dissolved in 10ml of deionized water to prepare a photoinitiator Irgacure 2959 solution, and the solution is stored for standby;
step (3) 1g of acrylamide is dissolved in 10ml of deionized water;
step (4) 0.04g of 3-acrylamidophenylboronic acid is dissolved in 1ml of methanol solution;
step (5) mixing the solutions in step (3) and step (4);
step (6) adding 0.05g of procyanidin powder into the solution prepared in the step (5);
step (7) adjusting the PH of the solution in step (6) to 8.5 by using the solution prepared in step (1);
step (8), dropwise adding the solution obtained in step (2) into the solution obtained in step (7) under the light-shielding condition;
step (9), 1g of polyvinyl alcohol is dissolved in 10ml of deionized water, and the solution is placed in a constant-temperature water bath kettle, heated and stirred at 90 ℃ for at least 2 hours, and after being stirred uniformly, the solution is taken out and cooled to room temperature to obtain a polyvinyl alcohol solution;
step (10) under the light-shielding condition, the solution in the step (8) and the solution in the step (9) are mixed with each other;
and (11) after the solution in the step (10) is uniformly mixed, pouring the solution into a specific quartz plate mold with the thickness of 100mm multiplied by 2mm, and placing the mold in an ultraviolet curing box for irradiation for 10min to obtain the phenylboronic acid-based glucose response antioxidant intelligent hydrogel dressing.
Example 6
A method for preparing a procyanidin sugar-loaded stimulated hydrogel, which specifically comprises the following steps:
step (1) dissolving 0.4g of sodium hydroxide in 10ml of deionized water to prepare sodium hydroxide solution, and storing for later use;
under the light-shielding condition, 0.001g of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone is dissolved in 10ml of deionized water to prepare a photoinitiator Irgacure 2959 solution, and the solution is stored for standby;
step (3) 1g of acrylamide is dissolved in 10ml of deionized water;
step (4) 0.04g of 3-acrylamidophenylboronic acid is dissolved in 1ml of methanol solution;
step (5) mixing the solutions in step (3) and step (4);
step (6) adding 0.01g of procyanidin powder into the solution prepared in the step (5);
step (7) adjusting the PH of the solution in step (6) to 10 by using the solution prepared in step (1);
step (8), dropwise adding the solution obtained in step (2) into the solution obtained in step (7) under the light-shielding condition;
step (9), 1g of polyvinyl alcohol is dissolved in 10ml of deionized water, and the solution is placed in a constant-temperature water bath kettle, heated and stirred at 90 ℃ for at least 2 hours, and after being stirred uniformly, the solution is taken out and cooled to room temperature to obtain a polyvinyl alcohol solution;
step (10) under the light-shielding condition, the solution in the step (8) and the solution in the step (9) are mixed with each other;
and (11) after the solution in the step (10) is uniformly mixed, pouring the solution into a specific quartz plate mold with the thickness of 100mm multiplied by 2mm, and placing the mold in an ultraviolet curing box for irradiation for 5min to obtain the phenylboronic acid-based glucose response antioxidant intelligent hydrogel dressing.
Example 7
A method for preparing a procyanidin sugar-loaded stimulated hydrogel, which specifically comprises the following steps:
step (1) dissolving 0.4g of sodium hydroxide in 10ml of deionized water to prepare sodium hydroxide solution, and storing for later use;
under the light-shielding condition, 0.001g of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone is dissolved in 10ml of deionized water to prepare a photoinitiator Irgacure 2959 solution, and the solution is stored for standby;
step (3) 0.4g AAPBA and 1gAM are put into a round bottom flask, 0.06g Azodiisobutyronitrile (AIBN) and 10ml dimethyl sulfoxide (DMSO) are added, vacuum is introduced and nitrogen is introduced to remove oxygen in the reaction environment for 3 times, and the reaction is carried out at 60 ℃ for 12 hours and then the mixture is taken out;
step (4), dripping the solution in the step (3) into an acetone solution to generate white precipitate, filtering and drying;
step (5) dissolving the powder prepared in step (4) with 10ml of deionized water;
step (6) adding 0.01g of procyanidin powder into the solution prepared in the step (5);
step (7) adjusting the PH of the solution in step (6) to 8.5 by using the solution prepared in step (1);
step (8), dropwise adding the solution obtained in step (2) into the solution obtained in step (7) under the light-shielding condition;
step (9), 1g of polyvinyl alcohol is dissolved in 10ml of deionized water, and the solution is placed in a constant-temperature water bath kettle, heated and stirred at 90 ℃ for at least 2 hours, and after being stirred uniformly, the solution is taken out and cooled to room temperature to obtain a polyvinyl alcohol solution;
step (10) under the light-shielding condition, the solution in the step (8) and the solution in the step (9) are mixed with each other;
and (11) after the solution in the step (10) is uniformly mixed, pouring the solution into a specific quartz plate mold with the thickness of 100mm multiplied by 2mm, and placing the mold in an ultraviolet curing box for irradiation for 5min to obtain the phenylboronic acid-based glucose response antioxidant intelligent hydrogel dressing.
Claims (8)
1. The preparation method of the procyanidin sugar-loaded stimulated hydrogel is characterized by comprising the following steps of:
(1) The 3-acrylamidophenylboronic acid (AAPBA) solution and the Acrylamide (AM) solution are mixed to obtain a molecular network of an AM-AAPBA compound;
(2) Preparing a high molecular polymer of polyvinyl alcohol (PVA), and then adding the high molecular polymer into an AM-AAPBA molecular network to enable hydroxyl of the PVA and a phenylboronic acid compound to form a borate dynamic covalent bond;
(3) Adding antioxidant procyanidine into the mixed solution, placing in dark condition, weighing, adding a certain amount of photoinitiator, and performing in-situ polymerization to obtain the final product.
2. The method of manufacturing according to claim 1, characterized in that: two different methods are used with respect to the molecular network for obtaining the acrylamide and 3-acrylamidophenylboronic acid complexes.
3. Two different methods of obtaining an AM-AAPBA molecular network according to claim 2 are respectively:
(1) After preparing an AM solution, directly adding AAAPBA with a certain mass into the solution, and stirring for a plurality of hours until the solution is uniform to obtain the AAAPBA;
(2) AAPBA and AM were added to a round bottom flask in different molar ratios, and appropriate amounts of Azobisisobutyronitrile (AIBN) and dimethyl sulfoxide (DMSO) were added, and the oxygen in the reaction environment was removed 3 times by vacuum and nitrogen filling, and after reaction at 60℃for 12 hours, taken out. The solution was dropped into an acetone solution. A white precipitate immediately formed, which was filtered and freeze-dried.
4. The method of manufacturing according to claim 1, characterized in that: the use of AAPBA set two reference amounts of 0.0001mol and 0.0002 mol.
5. The method of manufacturing according to claim 1, characterized in that: since the formation of the borate bond is performed under the weak alkaline condition, the pH of the whole solution should be adjusted to 8.5-10 after AM, AAPBA, PVA is completely added.
6. The method of manufacturing according to claim 1, characterized in that: irgacure 2959 is used in the present invention, the photoinitiator concentration being 1-2X 10 -3 g/ml。
7. The method of manufacturing according to claim 1, characterized in that: the phenylboronic acid-based glucose response antioxidant intelligent hydrogel dressing is formed by in-situ polymerization under ultraviolet light, so that the ultraviolet light irradiation time is controlled.
8. The method of manufacturing according to claim 1, characterized in that: the swelling of the phenylboronic acid-based glucose-responsive antioxidant smart hydrogel dressing was also explored using simulated external glucose concentrations of 0mg/ml, 2mg/ml, 4mg/ml, 10mg/ml, and with respect to the release of procyanidins.
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